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Mechanistic views on aromatic substitution reactions by gaseous cations
Author(s) -
Fornarini Simonetta
Publication year - 1996
Publication title -
mass spectrometry reviews
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.035
H-Index - 126
eISSN - 1098-2787
pISSN - 0277-7037
DOI - 10.1002/(sici)1098-2787(1996)15:6<365::aid-mas2>3.0.co;2-g
Subject(s) - chemistry , reactivity (psychology) , kinetic isotope effect , electrophile , cationic polymerization , computational chemistry , substitution reaction , ionic bonding , electrophilic aromatic substitution , electrophilic substitution , medicinal chemistry , organic chemistry , ion , catalysis , deuterium , medicine , physics , alternative medicine , pathology , quantum mechanics
Recent advances in the understanding of the gas‐phase reaction of aromatics with cationic electrophiles in a thermally equilibrated domain are described. The overall substitution reaction is analyzed in terms of its elementary steps. Their contribution to the overall reactivity pattern is dissected by the use of selected systems, which allowed one to highlight the kinetic role of single elementary events. Mechanistic studies have focused on the structure and reactivity of covalent and non‐covalent ionic intermediates, which display a rich chemistry and provide benchmark reactivity models. Particular interest has been devoted to proton transfer reactions, which may occur in either an intra‐ or intermolecular fashion in arenium intermediates. A quantitative study of their rates and associated kinetic isotope effects is reported. © 1997 John Wiley & Sons, Inc. Mass Spectrom Rev 15(6), 365–389, 1997